Electrolytic cell



C W. MARSH ELECTROLYTIC CELL Filed April 7, 1924 2 Sheets-Sheet 1 A TTORNEYS Oct. 27, .1931.

Oct. 27, 1931. c. w. MARSH ,3

ELECTROLYTIC CELL Filed Apri l 7, 1924 2 Sheets-Sheet 2 A TTORNEYS Patented Oct. 27, 1931 UNITED STATES CLARENCE W. MARSH, OI COSCOB, COI I'NECTICUT ELECTROLYTIC CELL Application filed April 7, 1924. Serial No. 704,640.

This invention relates to electrolytic units particularly adapted to the manufacture of chlorine gas for various usages, such as the treatment of water, industrial or sewerage Waste, air, gas, or for purposes of disinfec tion, sterilization, deodorization and the manufacture of hypochlorite solutions and otherchlorine compounds of sodium.

An object of the invention is to provide an improved apparatus for this purpose .which is practical, economical and efficient for the generation of small quantities of chlorine gas, and dosing it accurately to water, fluids, liquids or other substances in regular or variable amounts; and with which the manufacture of fresh Dakin solution, hypochlorite solutions or other various chlorine compounds of sodium is made economical, convenient and feasible as well as inexpensive.

A further object is to provide an improved electrolytic cell of such simple and inexpensive structural features that such cells or groups of cells can be replaced with new cells when worn out, more economically than they can be repaired or rebuilt.

A further object is to provide an improved cell which may operate on a low amperage and voltage in connection with the forms of the various types ofsmall rectifiers now on the market, at the same time being comparatively inexpensive, efficient, practical, light, compact, of low maintenance and cost, and which may operate over comparatively long periods of time without attention.

A further object is to provide an improved cell in which the internal resistance and polarization by gas bubbles, will be considerably reduced especially at the higher ourin groups to deliver the desired quantity of chlorine gas.

Various other objects and advantages will be apparent fromthe following. descri tion of embodiments of the invention, an the novel features will be particularly pointed out hereinafter in claims.

In, the accompanying drawings:

Fig. 1 is an elevation somewhat diagramrent densities, and which may be combinedmaticand partially in section of an electrolytic unit constructed in accordance with the invention.

Fig. 2 is asectional view of an electrolytic cell constructed in accordance with the invention but illustrating a modification of the type of cell shown in Fig. 1.

Fig. 3 is an elevation of apparatus for making a fresh hypochlorite solution such as '3 which may be formed of any suitable insulating material such as asbestos board, hard rubber, or asphaltic compounds. A diaphragm sheet 4 is wrapped around the anode and spacing rings any desired number of tlmes so as to ppovide an encasing shell or cylinder of a thickness corresponding to the 7 combined thickness of the layers and spaced from the anode by the rings. This sheet dlaphragm may be of any suitable material commonly used in electrolytic cells, such as asbestos paper and various parchment so papers.

The cathode 5 "comprises a longitudinally slit tubular metal shell formed of perforated sheet metal, which is adapted to embrace the anode and diaphragm constructed as just ezrplalned. The shell, along the edges of the $116, is provided with clamping ears 6 and corresponding ears upon opposite sides of the slit are connected by clamping screws 7. When the screws 7 are tightened, the cathode shell will be contracted and tightened so as to be clamped over the diaphragm and secure it to the anode and spacing rings 2 and 3. A terminal conductor 8 of suitable material such as lead, is connected into one end of the anode 1, and projects to some iagtent from the end of the anode as shown in The end of the anode having this connector and the periphery of the connector for some distance from the anode are preferably adhering material such as an asphaltic cement or paint. A disk 10 of suitable insulating material such as asbestos board, is placed over the connector 8, and fitting snugly within the diaphragm 4, but having an aperture 11 surrounding the connector 8 of a larger diameter or width than the diameter of the connector, so as to provide a space leading to the end of the anode.

A tube 12 of suitable insulating material such as hard rubber, glass or porcelain,

passes through and is secured in the disk 10 near its periphery and extends endwise therefrom. The aperture 11 in the disk 10 is then filled with a suitable insulating material 13 such as plastic asphalt or asphaltic cement which will adhere firmly to the coating 9 upon the connector and the end of the anode 1.

A conductor 14 is secured to the outer end of the connector 8, and the end of the oathode shell outwardly of the disk 10, is filled with an insulating material 15, such as a plastic asphalt or asbestos cement or of any of the wax or tarry fillers commonly used, for example, as a seal for the ends of dry battery cells. Preferably, the portions 13 and 15 which fill the aperture 11 in the disk 10 and the outer end of the cathode shell, may be poured or placed at the same time and form one integral part, which thus elimmates one extra operation.

A disk 16 of suitable insulating material such as asbestos board, is placed within the diaphragm and cathode shell at the opposite end of the anode, and is provided with an aperture or recess 17 into which a pin on the end of the anode may extend so as to assist in spacing that end of the anode from the diaphragm. i

The end of the cathode shell, outwardly fromthe disk 16, is then filled and sealed with a suitable insulating material such as asphaltic cement or plastic asphalt.

The material ofthe cathode shellmay be the same as commonly employed for oath-- odes in electrolytic cells such as nickel or iron' but preferably nickel is utilized because the electrolyte and the caustic soda produced by the electrolytic action will not corrode or materially affect the nickel. The cathodes, are perforated or reticulated for the passage of the hydrogen and caustic soda and, if iron is used as the material of the cathode, it will rust and corrode during periods of inactivity of the cell, the corrosion and rusting soon filling the apertures in the cathode and interfering with the passage of the caustic soda and hydrogen. With cathodes of nickel or with nickel surfaces, there will be little or no corrosion and never sufficient to fill the apertures during the periods of inactivity of the cells and, therefore, such a cell, when conductors 14 and 19 are connected to a suitable panel board 20, upon which suitable regulating mechanism such as a resistance device 21 and ammeter 22 may be mounted for controlling and indicating the quantity of current passing to the cell. Conductors 23 and 24 connect the panel board with any suitable rectifier, and the rectifier is then connected by wires 26 to a plug 27 for connection to any source of current.

The tube 12 is connected through a detachable connection 28 to a branch passage 29 in a supply conduit 30, and the cell and conduit are preferably supported in inclined positions as shown in Fig. 1. The lower end of the supply conduit 30 is connected by a pipe 31 to the lower part of a well 32, in the upper end of which is immersed the neck or mouth 33, of an' inverted bottle or container 34 containing a supply of electrolyte. The electrolyte will flow from the bottle or container 34 into the well 32, until the level of the electrolyte reaches the mouth of the container inverted therein, at which time the electrolyte in the well will serve as an air seal preventing the escape of further electrolyte from the container until the level of the electrolyte in the well falls so as to open the mouth of the con-' tainer.

The electrolyte will flow from the well through the conduits 31 and 30 until the level in the latter corresponds with the level in the well. The supply conduit 30 is so positioned that the normal level of the electrolyte therein will be above the branch 29 leading into the interior of the cell, in order that the electrolyte from the supply conduit will pass through the. branch 29 and the tube 12 into the chamber in the electrolytic cell, it being understood that the spacing ring 3 isprovided with an aperture or notch 35 permitting the passage of the electrolyte from the tube 12 to the space between the anode and the diaphragm. In this manner, the interior of the cell will be automatically maintained and filled under 7 a constant head. If desired, the corner edge of the anode may be cut away as at 36to provide necessary clearance or space for the passage of electrolyte from the tube 12 to the interior of the cell.

When a current is passed through the cell, an electrolytic action, well known in the art, will occur, in which the electrolyte, common- 1y of salt solution, will be decomposed into chlorine gas and caustic soda. The chlorine gas will be liberated in the space between the anode and diaphragm and will rise and pass out through the tube 12 and the branch conduit'29 into the supply conduit 30, and then rise therein, entering a conduit 37, which rises to a height above the level of the electrolytein the well, so that nothing but gas will pass through this conduit. The caustic soda will collect upon the cathode'shell and run down the same to the lowermost corner edge and then drip into a suitable container or receptacle 38. An enclosing shell for the cathode may of course be provided if desired.

The conduit 37 is connected to a point of delivery of the chlorine gas,'but in Fig. 1, this conduit is connected to the suction side of an injector device 39 through which a stream of fluid is passed by means of a pipe 40, the gas and fluid mixture being dischar d therefrom through the pipe 41. This flui is preferably the water or liquid to be-treated,

and by its velocity creates a suction which will draw the chlorine gas collectin in the 'conduit37 into the injector device an thence with the injector fluid to a tank or other point ofdisposal. This apparatus maybe used for adding chlorine gas to swimmin tanks. or water supply systems, but in many ,casesit is desirable to also add a hypochlorite solution. Accordingly a'suitable substance such as caustic soda or sodium carbonate may be conducted from a a supply container 42 throu h a controlling device 43 to the conduit 37 be ore it enters the injector device, and

this sodium carbonate or caustic soda solution entering the conduit 37, will react withthe chlorine as therein and form the h poas one opening automatically against the ac-. tion of a spring to admit air to the conduit when the sugtion in the conduitexceeds a definite amount which may be varied by varying the stress in the s ring.

In Fig. 2, a modiv ed embodiment of the 3 cell is illustrated. The diaphra m 44 is arranged along the inner surface 0 the cathode shell 45, and one end of the sh'elljand diaphragm is closed by a disc 46 of suitable insulating material, such as asbestos board,

and-the terminal connector 47 is anchored in the anode 48 in the same manner as explained in connection with Fig. 1. If desired, a shell,

- 49' of suitable insulating material such. as

hard rubber, may be provided around the projecting end of the connecter 47. The connector 47 and its protecting sleeve 49, project through the disc 46 and the conductor 14 is connected thereto. A supply conduit 50 has a pair of branches 51 extending laterally' therefrom, and this conduit is su ported so that its branches 51 extend throng an aperture in the disc 46 and communicate with the interior of the cell. A head of suitable insulating material such as asphaltic cement, plastic vasphalt, or other insulating plastic compounds, is then placed around the supmay have its ends formed within the head 52, but the casing should have a vent 53 for the escape of hydrogen gas which is formed during the electrolytic process. 1 I

The inner end of the anode is supported by an insulating pin 54 from a disc 55 of suitable insulating materialsuch as asbestos board, which is fitted into the corres ondin end of the diaphragm and cathode s ell. closure 56 of material similar to the head 52 is formed about the cathode shell and diaphragm and against the disk 55' so as to effectively seal that end of the cathode shell. A conductor 19 may be connected to the cathode shell so as to be embedded in the head 52, or so as to pass through the-cas- -mg-53. A valve or a cook 57 is provided in ply conduit 50' and its branches as well' as against the disc 46 so as to seal that end of f the cell. If desired an enclosing casing 53 shown in Fig. 1 except that in Fig. 1, the electrolyte enters the interior of the cell through the same opening that the chlorine gas passes through 111 leaving the cell, whereas in the i type of cell shown in Fig.2, the electrolyte will enter through both of thebranch con-' dults 51 and the chlorine gas will-leave the cell through the uppermost of the branch conduits.

In Figs. 3 and 4, I have illustrated a ratus by WhlCh the manufacture of 'Dakin solution, hypochlonite solutions, or

various other compounds,may be carried on ma very slmple, continous, inexpensive, and practical manner. In this apparatus, I have illustrated an electrolytic cell of the type shown inFig. 1 with the same means of su plylng a constant supply of electrolyte to tl ie cell and thus maintain the electrolytic cham-- ber completely filled. The chlorine gas collecting in the conduit 37a corresponding to v the conduit 37 of Fig. 1, will'be conducted upwardly to a point above the level of the electrolyte in the well and then downwardly through a pipe or conduit 58 to a point below the. lowermost part of the electrolytic cell where it enters a T conduit 59 to one branch ofwhichxa coil or react-ion tube-60 is con-- j controlledby the valve 64, is connected to one branch of a T conduit 59, another branch of this T conduit connects with the T conduit 59 so that the reaction solution from the well 61, will enter the T conduit 59 and pass therefrom into the T conduit .59 and mix with the chlorine gas, thetwo then passing downwardly into and along the reaction tube 60. This reaction tube or pipe 60 is arranged in a position substantially horizontal, so that the mixture of the chlorine gas and-the reaction solution will pass slowly along the same to aflord sufficient opportunity for the reaction to occur, the product being dis-' charged at 65 into any suitable container 66. The valve 57 in the conduit 37* serves by the admission of some air to vary the amount of chlorine entering the reaction tube and also prevents the application of too strong a suction upon the electrolytic cell chamber.

In many instances, a pure product is not necessary and therefore the caustic soda re sulting from the electrolytic action may be utilized to supply at least a portion of the reaction liquid. I have illustrated a con nection 67 between the receptacle 38, in which the caustic sodais collected from the electrolytic cell, and the T conduit 59'? through which the reaction liquid passes to the T conduit 59. In some cases, the canstic soda supplied by the electrolytic action may not be sufiicient to combine with the chlo rine gas liberated, but by regulating the valve 64, suflicient additional reaction fluid soda, the connection between the conduit 67 duit, a source of electrolyte supply connected may be allowed to mix with the caustic soda to supply the desired quantity .of reaction fluid. If it is desired not to use the caustic and receptacle 38 may be interrupted or the conduit 67 closed. More or less of the'salt solution in the cell may pass through the diaphragm and mix with the caustic soda formed by the electrolytic action, but in many instances, the salt solution will not be objectionable in the final product.

The reaction liquid from the well 61, the caustic soda from the electrolytic cell, or both, enters the inclined conduit 58 before it reaches its lowest level and connects with the reaction tube 60 so that the liquid entering" conduit 58 and then passing downwardly will create a slight suction upon the conduit 37 and draw over the chlorinegas which has been accumulating in the conduit 37 When the electrolytic cell is arrangedwith its axis inclined to the horizontal, the chlorine gas-will rise in bubbles and pass directly to the upper part of the cathode and then along the same to the outlet, instead of passing along the surface of the anode as is the case when such cells are .in a strictly vertical position. The gas bubbles, in passing along the narrow strip of the cathode or diaphragm,

will. not materially increase'internal resistance of the cell by polarization since the surface of the anode will be practically free of current densities. It will be understood thatany number of these electrolytic cells may be connected in parallel to a common supply conduit or to a common well and in series, parallel, or series-parallel in an electric circuit, thus giving any desired quantity production of gas, with a minimum of necessary apparatus. By utilizing the supply conduit for the removal of the gas and for maintaining the cell completely filled with electrolyte, a gas chamber in the cell will be unnecessary.

It will be understood that the details and arrangements of parts, which have been herein described and illustrated for the purpose of explaining the nature of the invention, may be varied and modified by those skilled in the art within the principle and scope of the invention as expressed in the appended claims.

I claim: I

1. An electrolytic unit comprising a cell having a cathode, an anode, and an inlet conduit leading downwardly into the uppermost part of the electrolytic chamber for supplying an electrolyte to the space between the anode and cathode and removing the gas "formed in said space, means including a supply conduit connected to the inlet conduit for maintaining automatically a level of the electo one end of the conduit, a gas removal conduit connected to the other end of the conduit. an electrolytic cell having a gas chamber, and a branch connection between the said conduit allfil the upper end of the gas chamber of said ce a 3. An electrolytic unit comprising a cell having a relatively long concentric anode and cathode, and means for su porting said cell with its anode and catho e making a considerable angle to the vertical, whereby the gasbubbles will move along the cathode and not'along the anode to any material extent.

4. An. electrolytic unit comprising a cell having a cathode, an anode, and an inlet con duit leading downwardly into the uppermost.

which the evolved gas may be removed from the interior of the cell.

6. An electrolytic cell comprising an anode, spacing rings of insulating material surrounding the ends of the anode, a diaphragm extending peripherally around the rings and anode and spaced from the,

anode by the rings, a longitudinally slit perforated cathode shell embracing the diaphragm and clamping it to the rings, means for adjusting the slit edges of the shell toward one another to provide the desired clamping action, a filler sheet in both ends of the cathode shell for closin the ends, and a tube passing through one o the end filler sheets through which the evolved gas may be removed from the interior of the cell, the ring at the end adjacent the tube having a electrolyte thereto and for the flow of gas therefrom, said conduit rising to a point substantially above the level of the cell, means for applying suction thereto, a reagent reservoir, a connection between said reservoir and conduit at a point intermediate the cell and suction means, and a barometric feed device connected to said conduit to maintain a liquid level at a point between its elevated portion and the cell.

In witness whereof, I hereunto subscribe my signature.

CLARENCE W. MA SH.

passage therethrough from face to face for establishing communication between the tube and the electrolytic chamber between the diaphragm and anode.

7.v A cell having an electrolyte chamber provided with a gas outlet, a conduit connected therewith and extending upward and downward with respect thereto, and means for automatically supplying liquid to the lower portion of said conduit comprising a barometric feed reservoir having a discharge opening above the level of said outlet and below the upper part of said conduit, and means for receiving gas from the upper portion of said conduit.

8. In an electrolytic apparatus, the combination of a cell, a conduit for supplying electroylte thereto and for the flow of gas therefrom, said conduit rising to a point substantially above the level of the cell, means for applying suction to the elevated ortion of said conduit and a valve in said e evated portion of the conduit for regulating the degree of suction,

9. In an electroyltic apparatus, the combination of a cell, a conduit for supplying electrolyte thereto and for the flow of gas therefrom, means for applying suction to said conduit, a reagent'reservoir, a connection between said reservoir and saidconduit at a point intermediate said cell and said suction means, and valve means for regulating the degree of suction. A

10. In an electrolytic apparatus, the combination of a cell, a conduit for supplying 

